Rapid-setting non-elastomeric polyurethane compositions prepared in the presence of an organic carbonate

ABSTRACT

Mixtures comprising a low molecular weight polyol having a functionality of from 3 to about 8, a liquid modifier compound having a boiling point above 150*C, such as an organic carbonate, a polyisocyanate and a non-amine-containing catalyst, instantly set, after a brief induction period, to a solid, dense, nonelastomeric polymeric product which can be demolded within a period of from less than about 1 minute to about 5 minutes.

United States Patent Olstowski et a1.

[451 Apr. 15, 1975 RAPID-SETTING NON-ELASTOMERIC POLYURETHANE COMPOSITIONS PREPARED IN THE PRESENCE OF AN' ORGANIC CARBONATE Inventors: Franciszek Olstowski, Freeport;

Donald B. Parrish, Lake Jackson,

both of Tex.

Assignee: The Dow Chemical Company,

Midland, Mich.

Filed: Dec. 17, 1973 Appl. No.: 425,399

Related U.S. Application Data Continuation-impart of Ser. No. 366,835, June 4, 1973, which is a continuation-in-part of Ser. No. 179,149, Sept. 9, 1971, abandoned.

U.S. Cl. 260/30.4 N; 260/18 TN; 260/30.2; 260/30.4 R; 260/30.8 R; 260/3l.6; 260/31.8 R; 260/33.2 R; 260/33.6 UB; 260/33.8 UB;

260/77.5 AP Int. Cl C08g 22/04 Field of Search 260/30.4 N, 32.2, 45.8 A,

[56] References Cited UNITED STATES PATENTS 3,102,875 9/1963 Heiss 260/77.5

3,143,517 8/1964 Heiss 260/18 3,401,144 9/1968 Britain 260/45.8

3,489,723 1/1970 Kraft 260/77.5

3,499,858 3/1970 Strassel 260/30.2 4/1973 Jones et al 260/31.8

Primary Examiner-Eugene C. Rzucidlo Attorney, Agent, or Firm.lames G. Carter; Raymond B. Ledlie 29 Claims, No Drawings RAPID-SETTING NON-ELASTOMERIC POLYURETHANE COMPOSITIONS PREPARED IN THE PRESENCE OF AN ORGANIC CARBONATE This application is a continuation-in-part of our copending application Ser. No. 366,835, filed June 4, 1973 which is a continuation-in-part of application Ser. No. 179,149, filed Sept. 9, 1971 now abandoned.

This invention relates to polyurethane compositions and more particularly relates to rapid-setting, solid, dense, non-elastomeric polyurethane compositions.

Rapid setting, dense, opaque polyurethane compositions have been taught in US Pat. No. 3,378,51 1. Such compositions employ, as one of the essential ingredients, a liquid plasticizer which is a dicarboxylic acid ester. These compositions while useful in many applications, have some disadvantages in that they are not readily paintable and are susceptible to degradation in such common solvents as acetone, methyl isobutylketone, methylene chloride, ethylene dichloride, ethyl acetate, tetrahydrofuran and the like.

The present invention provides one or more of the following advantages over the prior art, i.e., improved detail reproduction in ornamental castings having intricate detail, improved paintability, improved solvent resistance, improved lubricity in cast gears and other machine elements and the like.

It is an object of the present invention to provide a rapid-setting, dense, rigid polyurethane composition.

Another object of the present invention is to provide rapid-setting, non-elastomeric, opaque polyurethane compositions.

A further object of the present invention is to provide rapid-setting, dense, non-elastomeric, transparent polyurethane compositions.

These and other objects will become apparent from a reading of the following detailed specification.

The present invention concerns a composition which comprises a polyether polyol, an organic polyisocyanate and a non-amine-containing catalyst for urethane formation, characterized in that it contains a liquid modifier compound having a boiling point above about 150C selected from the group consisting of hydroxylcontaining and non-hydroxyl-containing polyoxyalkylene compounds, ester-modified polyoxyalkylene compounds, fatty acids, naturally occurring fatty oils, organic phosphates, organic phosphites, organic phosphonates, cyclic ethers, non-ester-containing aromatic compounds, partially hydrogenated aromatic com-' pounds, organic carbonates, halogenated aliphatic compounds, cyclic sulfones and mixtures thereof.

All the liquid modifier compounds have at least two points in common. They are (1 an apparent ability to act as a heat sink to prevent excessive bubbling which would result from the heat generated by the exothermic heat of reaction and (2) they have boiling points at atmospheric pressure above about 150C.

The term non-elastomeric polyurethane as employed herein is defined as a polyurethane product having an elongation value of less than 80 percent and the term dense is defined as a density of at least about 1 gram/cc.

Non-elastomeric, rapid-setting, polyurethane compositions are obtained by intimately admixing together a composition comprising A. a polyether polyol which is the adduct of a polyhydric initiator compound having a functionality of from 3 to about 8 with a vicinal epoxy compound,

said polyol having a hydroxyl equivalent weight of at least about and less than about 230; B. an organic polyisocyanate;

C. a liquid modifier compound having a boiling point above about C at atmospheric pressure including for example hydroxyl-containing and non-hydroxyl-containing polyoxyalkylene com-' pounds, fatty acids, naturally occurring fatty oils, organic phosphates, organic phosphites, organic phosphonates, cyclic ethers, non-ester containing aromatic compounds, partially hydrogenated aromatic compounds, organic carbonates, halogenated aliphatic compounds, cyclic sulfones, and mixtures thereof in any combination, and

D. a non-amine containing catalyst for urethane formation;

and wherein Components (A) and (B) are present in amounts so as to provide an NCOzOH ratio of from about 0.8:1 to about 2:1 and preferably from about 0.95:1 to about 1.121; Component C is present in quantities of from about 20-50% and preferably from about 30-50% with the proviso that when component (B) is a prepolymer containing less than about 40% NCO groups by weight, then component (C) is present in quantities of from about 10% to about 50% by weight of the sum of Components (A), (B), and (C); and (D) is present in quantities of from about 0.2 to about 10%, preferably from about 0.2 to about 3%, and most preferably from about 0.5 to about 3% by weight of the sum of the weights of Components (A), (B) and (C); with the proviso that when Component (C) is a halogenated aliphatic compound, it is employed in a range of from about 0.2 to about 50 percent by weight of the sum of the weights of Components (A), (B) and (C); that when the halogenated aliphatic compound also contains hydroxyl groups and has an 01-1 equivalent weight of less than about 500, it is employed in quantities of from about 0.2 to about 5 percent by weight based upon the sum of the weight of Components (A), (B) and (C), and that when Component (C) is a non-estercontaining aromatic compound or a halogenated aliphatic compound, the non-amine-containing catalyst, Component (D), is employed in quantities of from about 0.01 to about 10 percent by weight of the combined weights of Components (A), (B) and (C).

Suitable initiator compounds having from 3 to 8 hydroxyl groups which can be employed to prepare the polyols (Component A) employed in the present invention include, for example, glycerine, trimethylolpropane, pentaerythritol, sorbitol, sucrose, mixtures thereof and the like.

Suitable vicinal epoxy compounds which may be reacted with the initiator compounds to prepare the polyols employed as Component A in the present invention include, for example, the lower alkylene oxides and substituted alkylene oxides such as ethylene oxide, 1,2- propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin, epibromohydrin, epiodohydrin,

styrene oxide,-mixtures thereof and the like. Suitable polyoxyalkylene compounds which may be employed as the liquid modifier compound (Component C) include, for example,

1. a liquid, totally-capped or non-hydroxylcontaining block or randomly formed polyoxyalkylene glycol represented by the general formula wherein R and R are independently selected from satnal anhydride of a saturated or unsaturated acyclic aliurated and unsaturated hydrocarbon groups having phatic, a saturated or unsaturated cyclic aliphatic, or

from about 1 to about 6, preferably from about 1 to aromatic polycarboxylic acid, halogenated derivatives about 3, carbon atoms; R R and R are indepenthereof and mixtures thereof, each R is a substituent dently hydrogen, an aryl group, an alkyl group or haloindependently selected from hydrogen atoms, an alkyl alkyl group, said alkyl or haloalkyl group having from radical having from 1 to 20 carbon atoms, ahalomethyl about 1 to about 2 carbon atoms with the proviso that radical, a phenyl radical, and a phenoxymethyl radical, when R R R is a haloalkyl group, it is present in an alkoxymethyl radical with the proviso that one of minor amounts, i.e., a ratio of from about 0 to about the R substituents must be hydrogen, R is hydrogen or percent of the total R R R, groups, and x x a saturated or unsaturated aliphatic group having from x are integers, such that the boiling point of the liquid 1 to carbon atoms, m has an average value of from capped polyalkylene glycol is above about 150C; about 1.0 to about 2.0, n has a value from about 1 to 2. a liquid partially pp block or r n mly about 5, x has a value from about 1 to about 8 and y formed polyoxyalkylene compound represented by the has a value of 1 or 2 and wherein said ester-modified general f rmula polyether compound has a hydroxyl equivalent weight II. R O-CH -CH O-CH CH O-CH CH H 2 t 2 I )xz 2 I 5 o t R R 1%) wherein R and R R ....R,, are an defined in formula I above about 500 when 3 or more hydroxyl groups are above and x x x, are integers, the sum of which present and when 2 hydroxyl groups are present, an avprovides the partially capped polyoxyalkylene com erage equivalent weight of above about 700 and when pound with a molecular weight of at least about 700; zero or one hydroxyl group is present a molecular 3. a liquid, block or randomly formed polyoxyalkylweight of above about 700. ene glycol represented by the general formula Suitable initiators which may be employed to prepare III. H(o-cH -cH)- (o-c1i -c1i) (o-cH -cH)-oH wherein R R WR, are as defined in formula I above the liquid polyoxyalkylene and ester-modified polyoxyand x x ....x,, are integers, the sum of which provides alkylene modifier compounds (Component C) of the the polyoxyalkylene glycol with an equivalent weight of present invention include compounds having from 1 to at leat about 700, and about 8 hydroxyl groups such as, for example, metha- 4. a liquid, random or block polyoxyalkylene polyol nol, ethanol, propanol, butanol, ethylene glycol, propyhaving a hydroxyl functionality of from 3 to about 8 lene glycol, butylene glycol, l,6-hexane diol, glycerine,

represented by the general formula trimethylolpropane, pentaerythritol, sorbitol, sucrose, IV. 2 C(O-cH HWO-CH M (don 2H9 01% wherein R R ....R,, are as defined in formula 1 above, mixtures thereof and the like.

Z is the residue of an initiator compound having from When the liquid modifier compound, Component C, 3 to about 8 hydroxyl groups, x,, x x are integers, is an ester modified polyether polyol, the initiator comthe sum of which provides the polyoxyalkylene polyol pound may also be and is preferably an adduct of the with a hydroxyl equivalent weight of at least about 500 above mentioned initiator compounds and one or more and q is an integer having a value of from 3 to about 8. of the following vicinal epoxide-containing com- Suitable ester-modified polyoxyalkylene compounds pounds, i.e., the initiator compound is a polyoxyalkylwhich may be employed as the liquid modifier comene compound having 1 to 8 hydroxyl groups, preferapound (Component C) include, for example, those liqbl 2 to about 3 or 4 hydroxyl groups.

uid ester-modified polyethers having a boiling point Suitable vicinal epoxide compounds which may be above about C represented by the ge e a fo reacted with the above mentioned initiator compounds II II v. A o {6-2 (0 Melan n-0% Ril v R R wherein A is the residue of an initiator or starting comto prepare the modifier compounds (Component C) pound having from 1 to about 8 hydroxyl groups, Z is employed in the present invention include, for examthe residue, excluding the carboxyl groups, of an interple, ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin, epihromohydrin, epiodohydrin, styrene oxide, mixtures hereof and the like. i

The liquid modifier compounds represented by for .nulae I-IV and methods for their preparation are well nown in the art, e.g., U.S. Pat. No. 2,448,664; US at. No. 2,425,755; US Pat. No. 2,782,240 and U.S. Pat. No. 2,5 20,61 1. Methods for the preparation of the quid modifier compounds represented by the formula are given in a copending application Ser. No. 67,233, .led Aug. 26, l9 70 by Robert W. McAda, Jr. for ES- FER-MODIFIED POLYESTER POLYOLS and in :15. Pat. No. 3,502,601.

Suitable non-ester containing aromatic compounds hich may be employed as the liquid modifier comriound having a boiling point above about 150C (Comonent C) in the present invention include, for example, straight and branch chain aliphatic, alkoxy and halogen substituted benzenes, aromatic substituted benene and aromatic ethers, such as, for example, proenyl benzene, propylbenzene, butylbenzene, ethyltoliene, butyltoluene, propyltoluene, diphenyl oxide, biphenyl, 0-, mand p-diethylbenzene, dodecylbenzene, ctadecylbenzene, bromobenzene, l-bromo-3- Eilorobenzene, l-bromo-4-fluorobenzene, 1-bromo-2- :dobenzene, l-bromo-3-iodobenzene, l-chloro-4- 'zuorobenzene, o-dibromobenzene, mdibromobenzene, o-dichlorobenzene, mdichlorobenzene, l,3-dipropoxybenzene, l-ethyl-4- propylbenzene, l-fluoro-4-iodobenzene, 4-bromo-oxylene, a-bromo-m-xylene, 4-bromo-m-xylene, a-chlo- Suitable partially hydrogenated multi-ring aromatic compounds which may be employed as the liquid modifier compound (Component C) in the present inven tion include, for example, 1,4-dihydronaphthalene, 1,- 2,3,4-tetrahydronaphthalene, mixtures thereofand the like.

Suitable fatty acids and naturally occurring fatty oils which may be employed as the liquid modifier compounds (Component C) in the present invention includes, for example, oleic acid, linoleic acid, linolenic acid, and the like. The fatty acids resulting from the hydrolysis of naturally occurring oils of animal and vegetable origin including for example, linseed oil, castor oil, tung oil, fish oil, soya oil and the like and such acids as are produced as byproducts in chemical processes including for example, tall oil, the byproduct resulting from the conversion of wood pulp to paper by the sulfate process, mixtures of any of the above and the like.

Also operable as the liquid modifier compounds are the naturally occurring fatty oils having boiling points above about 150C including, for example, linseed oil, castor oil, tung oil, fish oil, soya oil, and the like.

Suitable organophosphorus compounds which may be employed as the liquid modifier compound, Component C, include, for example, organo phosphates, organo phosphites and organo phosphonates having boiling points above about 150C.

Organo phosphates, phosphites and phosphonates which may be employed as the liquid modifier compound include those liquid compounds represented by the formulae ro-m-xylene, 4-ethyl-m-xylene, S-ethyl-m-xylene, 2- bromo-p-xylene, a-chloro-p-xylene, 2-ethyl-p-xylene, 2-ethyl-p-xylene, o-bromo-toluene, m-bromotoluene, o-, m-, and p-chlorotoluene, tertiary butylstyrene, a-bromostyrene, B-bromostyrene, a-chlorostyrene, ,B-chlorostyrene, mixtures thereof and the like.

The above compounds may be represented by the following general formula provided it is understood that such compounds represented by the formula are liquids and have boiling points at atmospheric pressure above about 150C.

phate,

wherein R R and R are independently selected from the group consisting of alkyl, alkoxyaryl, aryloxyaryl, alkaryl, aralkyl groups and halogen substituted derivatives thereof. Y is oxygen or sulfur, X is a halogen, i.e., chlorine, fluorine, bromine or iodine, n has a value of 1 or 2. Suitable such compounds include, for example, tri-n-butyl phosphate, triethylphosphate, tricresylphostris-(beta-chloroethyl)phosphate, tris-(2,3- dibromopropyl)phosphate, butyl dichlorophosphate, 2-chloroethyl dichlorophosphate, ethyl dichlorophosphate, diethyl fluorophosphate, bis(2-chloroethyl) fluorophosphate, dibutyl chlorophosphate isoamyl dichlorothionophosphate, ethyl dibromothiophosphate, 2-chlorophenyl dichlorophosphate, 2-methoxyphenyl dichlorophosphate, 2-phenoxyphenyl dichlorophosphate, 2-chloroethyl dichlorophosphite, tris( 2-chloroethyl)phosphite, tributyl phosphite, tricresyl phosphite, triethyl phosphite, diethyl isoamylphosphonate, diethyl ethylphosphonate, dimethyl methylphosphonate, diethyl methylphosphonate, diisobutyl isobutylphosphonate, bis(2-bromopropyl)-2-bromopropane phosphonate.

When haloor dihalo-phosphates or phosphites or their thiono derivatives are employed as the liquid modifier compound (component C), they are preferably added to the composition just prior to the nonamine-containing catalyst so as to minimize their reaction with the hydroxyl groups of the polyol, component The organo phosphorus compounds may be prepared by procedures described in ORGANO-PHOSPHORUS COMPOUNDS, G. M. Kosolapoff, John Wiley and Sons, lnc., 1950.

Suitable liquid organic carbonates which may be employed as the liquid modifier, component C, in the present invention include the acyclic and cyclic carbonates represented by the formulae R -Cw-C-P I I wherein each R and R are independently aryl, alkyl (having from about 1 to about 6 carbon atoms) or alkenyl groups (having from about 1 to about 6 carbon atoms) and substituted derivatives thereof and each R and R are selected from the same groups as R, and R and hydrogen.

Suitable liquid acyclic organic carbonates which may be employed in the present invention include, for example, bis( 2-chloroethyl)carbonate, di-n-butyl carbonate, butyldiglycol carbonate, cresyldiglycol carbonate, dibutyl carbonate, di-2-ethylhexyl carbonate, dimethallyl carbonate, dinonyl carbonate and the like. The organic acyclic carbonate may be prepared by procedures given in US. Pat. No. 2,687,425.

Suitable liquid cyclic organic carbonates include, for example, propylene carbonate, butylene carbonate, styrene carbonate, mixtures thereof and the like. The cyclic organic carbonates may be prepared in the manner described in Canadian Pat. No. 556,006.

Suitable cyclic polyethers which may be employed as the liquid modifier (component C) include, for example, the cyclic tetramer of ethylene oxide, cyclic pentamer of propylene oxide, cyclic tetramer of propylene oxide, mixtures of the above and mixtures of cyclic pentamers and above of ethylene oxide and or propylene oxide. Any liquid cyclic polyether having a boiling point above 150C may be employed as the liquid modifier in the present invention including cyclic polyethers prepared from butylene oxide, epichlorohydrin and the like.

The liquid cyclic polyether'modifier compounds may be prepared by procedures mentioned in Cyclic Polyethers and Their Complexes with Metal Salts by C. J. Pedersen, J. Am. Chem. $00., Vol. 89, p. 7017-7036, 1968, Twelve-Membered Polyether Rings. The Cyclic Tetramers of Some Olefin Oxides by R. S. Kern; J. Org. Chem., Vol. 33, p. 388-390, 1968; British Pat. Nos. 785,229 and 1,108,921.

Suitable halogenated aliphatic compounds having a boiling point above about 150C which may be employed as the modifier compound in the present invention include, for example, tetrabromoethane, bromoform, hexachlorobutadiene, tetrachlorobutadiene, l ,2,3,3-tetrachlorobutane, 1 ,S-dibromo-pentane, 1,1,2-tribromopropane, l,2,3-trichloropropene,

polyepichlorohydrin diol having an equivalent weight above about 700 up to about 4,000, chlorinated paraffins, e.g. Chlorowax No. 40, l-mercapto-3- chloropropanol-2, 3-chloropropane-l ,2-diol, 2-chloropropane-1,3-diol, 1,3-dichloro-2-propanol, mixtures thereof and the like.

The halogenated aliphatic compounds which do not contain hydroxyl groups may be employed in quantities of from about 0.2 to about 50 percent by weight of the sum of the weights of components A, B and C, and preferably from about 1 to about 10 percent by weight on the same basis, i.e., the sum of the weights of components A, B and C. When the halogenated aliphatic compounds employed herein also contain hydroxyl groups and have a hydroxyl equivalent weight of less than 500, the quantity which is to be employed is from about 0.2 to about 10 and preferably from about 0.4 to about 5 percent by weight based upon the combined weights of A, B and C.

Suitable cyclic sulfones which may be employed as the liquid modifier compound include the S-membered cyclic sulfones such as, for example, 3-methylsulfolane (3-methyltetrahydrothiophene-l l -dioxide) and the like.

The term liquid modifier boiling above about C includes eutectic mixtures of the previously described classes of compounds which are solids at atmospheric pressure but said eutectic mixtures are a liquid at room temperature and atmospheric pressure which have boiling points above about 150C. Also included in the definition are those solid compounds of the classes previously described which are dissolved in a liquid member of any of the described classes of compounds having boiling points above about 150C wherein the resultant solution is a liquid at standard conditions of temperature and pressure and have boiling points at atmospheric pressure above about 150C.

Suitable non-amine-containing catalysts for urethane formation include, for example, organo-metal compounds of tin, zinc, lead, mercury, cadmium, bismuth, cobalt, manganese, antimony, iron and the like such as, for example, metal salts of a carboxylic acid having from about 2 to about 20 carbon atoms including, for example, stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, ferric acetylacetonate, lead octoate, lead 'oleate, phenylmercuric propionate, cobalt naphthenate, lead naphthenate, mixtures thereof and the like.

It is preferred that the catalysts be employed in liquid fonn. Those catalysts which are not ordinarily liquids may be added as a solution in a solvent which is compatible with the other components employed in the composition of the present invention. Suitable such solvents include, for example, dioctylphthalate, polyoxyalkylene glycols, mineral spirits, dipropylene glycol, mixtures thereof and the like.

It has previously been stated that the quantity of the non-amine-containing catalyst is in the range of from about 0.2 to about 10%. However, when the liquid modifier compound is a non-ester-containing aromatic compound or a halogenated aliphatic compound as described herein, the operable range for the quantity of the catalyst to be employed is from about 0.01 to about 10% and preferably from about .05 to about 2% and most preferably from about 0.1 to about 0.5% by weight based upon the combined weights of Components A, B and C.

Suitable polyisocyanates which may be employed as Component B in the compositions of the present invention include, for example, any organic polyisocyanate having 2 or more NCO groups per molecule and no other substituents capable of reacting with the hydroxyl groups of the polyoxyalkylene compound. Suitable such polyisocyanates include, for example, 2,4- toluenediis'ocyanate, 2,6-toluenediisocyanate, hexamethylene diisocyanate, p,p'- diphenylmethanediisocyanate, pphenylenediisocyanate, hydrogenated methylene diphenyldiisocyanate (e.g. l-lylene W) naphthalene diisocyanate, dianisidine diisocyanate, polymethylene polyphenyl-isocyanate, mixtures of one or more polyisocyantes and the like.

Other organic isocyanates which may suitably be employed and which are to be included in the term organic polyisocyanate include isocyanate terminated prepolymers prepared from the previously mentioned polyols and the above mentioned isocyanates.

The cured compositions of the present invention vary from transparent solids to white or off-white opaquesolids, depending upon the particular liquid modifier compound (component C) and/or polyisocyanate (component B) employed to produce such compositions.

Suitable modifier compounds which may be employed to produce solid opaque products include, for example,

1. those compounds represented by formula I wherein at least by weight of the compound is derived from units wherein R R ....R,, are hydrogen.

2. those compounds represented by formula II wherein the molecular weight is at least about 1,500;

3. those compounds represented by formula III whrein the molecular weight is at least about 3,000; and

4. those compounds represented by formula IV wherein the molecular weight is at least about 7,000 and at least 20% of the molecular weight is derived from units wherein R R ....R, are hydrogen.

Suitable modifier compounds which may be employed to produce transparent solid products include, for example,

1. those compounds represented by formula I wherein less than about 20% by weight of the compound is derived from units wherein R R ....R, are hydrogen;

2. those compounds represented by formula II wherein the molecular weight is greater than about 700 but less than about 1,500 and wherein less than 207 of the molecular weight is derived from units wherein R R ....R,, are hydrogen;

3. those compounds represented by formula I wherein the molecular weight is greater than about 700 and less than abut 3,000 and wherein less than about 20% of the molecular weight is derived from units wherein R,, R ....R, are hydrogen; and

4. those compounds represented by formula IV having a molecular weight from about 1,500 to less than about 7,000 and wherein less than about 20% of .the molecular weight is derived from units wherein R R ..;.R,, are hydrogen.

Rigid polyurethane products can be prepared by rapidly mixing the components of the compositions of the present invention. It is preferred to thoroughly blend together the components represented by A, the polyol,

about B, the polyisocyanate and C, the liquid modifier compound and then mixing the resultant mixture with Component D, the catalyst. Mechanical dispensing or combination mixing-dispensing devices can be employed by utilizing 2 or more streams of the individual components or mixtures of the components which are introduced into said device.

Other components including inert fillers such as, for

example, sand, microballoons, glass fibers, asbestos,

aluminum granules, silicon carbide powder and the like, coloring agents, such as pigments and dyes including, for example, chromic oxide, ferric oxide, mixtures thereof and the like may be employed in the compositions of the present invention without detracting from the scope thereof.

The compositions of the present invention rapidly produce solid products which may be demolded, i.e., the articles produced therefrom may be removed from the mold, within about 5 minutes, usually within about 3 minutes and preferably within about 1 minute or less from the time the catalyst is blended into the mixture and do not require the application of external sources of heat to accomplish this, although in some circumstances it may be desirable to post cure, at elevated temperatures, the products in order to develop certain properties. The compositions of the present invention not only can be demolded within 5 minutes and often in less than 2 to 3 minutes, but the cast objects produced therefrom have developed sufficient strength properties to be employed immediately upon cooling to room temperature for their intended purpose. The cast objects are hot or warm to the touch immediately after removing from the mold due to the exotherm generated during the reaction. This is a valuable contribution to the urethane molding art, in that productivity can be increased employing a given quantity of molds.

The choice of the catalyst involves the desired time delay between the catalyst being mixed into the reagents and the liquid mix instantly solidifying. For example, if tolylene diisocyanate is used along with a polyol that is the reaction product of glycerine with propylene oxide and having a molecular weight of about 260 plus a polyoxypropylene glycol having a molecular weight of about 4000 as the liquid modifier compound, then the addition of about 1% stannous octoate catalyst will yield a delay or induction time of 10 seconds before the mixture suddenly freezes into a solid. Substitution of dibutyltin dilaurate at the same catalyst level stretches this delay time to about 20 seconds, and phenyl mercuric propionate exhibits a delay time of about seconds before extremely rapid solidification occurs.

The change of isocyanate to a less reactive one, i.e., the substitution of hexamethylene diisocyanate for tolylene diisocyanate, correspondingly increases the delay time before rapid solidification takes place.

Suitable materials from which adequate molds, for casting the compositions of the present invention, may be prepared include polymers such as, for example, polyethylene, polypropylene, their copolymers and the like, polyurethanes, polysiloxane elastomers, Mylar, cured polyepoxides, mixtures thereof and the like.

lt is preferred to employ relatively thin wall molds or molds having a low heat capacity or thermal conductivity. Heavy molds made of relatively high thermal conductivity materials such as aluminum, copper, iron or steel and the like may present curing problems, i.e., the

reactants may not be readily demolded unless the mold is preheated to about 5090C, especially when casting relatively thin sections. However, high thermal conductivity materials such as copper or aluminum can be employed as thin wall molds without preheating if the thermal capacity of the mold is relatively low compared to the amount of heat liberated in the casting.

The compositions of the present invention are useful as, but not restricted to such uses as, a casting material for preparing bearing surfaces, annular spacers, decorative objects, furniture or furniture components, gears or other machine components, threaded protective plugs and caps, and the like.

The following examples are illustrative of the present invention but are not to be construed as to limiting the scope thereof in any manner.

The following examples 1-10 are illustrative of solid, rigid, opaque and translucent products.

EXAMPLE I A. An Examle of the Present Invention In a suitable container were thoroughly blended 30 grams of Voranol CP-260 (the reaction product of glycerine with propylene oxide having a molecular weight of about 260) as the polyol, 30 grams of P-4000, a polyoxypropylene glycol having a molecular weight of about 4000, as the liquid modifier compound and 30 grams of Hylene TM (an 80/20 mixture by weight of the 2,4- and 2,6-isomers of tolylene diisocyanate having an NCO equivalent weight of about 87).

After the above components were well mixed, 1 cc of a liquid dibutyltin dilaurate, commercially available as T-l2 catalyst from Metal and Thermit Corp., was rapidly stirred in and the resultant mixture was poured into a polyethylene beaker. Thirty seconds after stirring in the catalyst, the mixture suddenly turned an opaque white color and underwent substantially instantaneous hardening. Sixty seconds after the catalyst was added, a rigid, hard, white, opaque polymer casting was demolded, i.e. removed from the polyethylene beaker, and was found to have a density of 1.055 grams/cc.

B. Comparative Demonstration Efiect of One-Tenth the Amount of Catalyst The same procedure and composition as in A above was employed except that 0.1 cc of the dibutyltin dilaurate catalyst was employed with the following results.

60 seconds after the catalyst was added, the mixture was still a transparent liquid.

120 seconds after the catalyst was added, the mixture was an opaque liquid.

180 seconds after the catalyst was added, the mixture hardened but was too tacky to be demolded.

400 seconds after the catalyst was added, the casting was demolded.

The product was found to be a warped, rigid, white, opaque solid that was filled with gross bubbles or gas cells. This casting had a density of 0.864 grams/cc.

C. Comparative Demonstration of Effect of Omitting the Liquid Modifier Same procedure as in A above employing 33 grams of the indicated polyol and 33 grams of the polyisocyanate. The mixture suddenly gelled after the catalyst addition; however within the next 4 minute interval, the cast polymer grossly swelled and generated copious quantities of internal gas bubbles and open fissures across the top surface of the casting. The cured polymer mass had a density of 0.56 grams/cc.

EXAMPLES EMPLOYING VARIOUS POLYISOCYANATES EXAMPLE 2 Same procedure as in Example 1A employing the following components: 33 grams of Voranol CP-260 as the polyol 33 grams of P4000 as the liquid modifier 50 grams of lsonate 143L (dimerized diphenylmethanediisocyanate having an NCO equivalent weight of about 144 and a functionality of about 2.25) 1 cc octaoate containing 24% Pb.

in less than 15 seconds after catalyst addition, the mixture suddenly solidified into a cream-colored, opaque, hard, rigid polymer which was demoldable within 40 seconds.

EXAMPLE 3 EXAMPLE 4 Same procedure as in Example lA employing the following components. 30 grams of Voranol CP-260 30 grams of P-3000 32 grams of Takenate 500 (Xylylene diisocyanate having an NCO equivalent weight of about 94 and an average functionality of about 2). 1 cc of lead octoate (24% Pb).

The mixture suddenly turned into an opaque, white solid within about 30 seconds and could be demolded within about 50 seconds.

EXAMPLES EMPLOYING VARIOUS POLYOLS EXAMPLE 5 Same procedure as in Example 1A employing the following components.

26 grams of Voranol CP45O (reaction product of glycerine with propylene oxide having a molecular weight of about 450).

15 grams of P-4000 16 grams of Hylene TM 1 cc of lead octoate (24% Pb) The mixture rapidly set to produce a rigid, hard, opaque, white, solid, casting within about 25 seconds which could be demolded within about 40 seconds.

EXAMPLE 6 Same procedure as in Example 1A employing the following components. 30 grams of the reaction product of glycerine with ethylene oxide in a molar ratio of 1:3 and having a hydroxyl equivalent weight of about 75.9. 30 grams P-4000 30 grams Hylene TM 1 cc lead octoate (24% Pb) The mixture suddenly set into a hard, rigid, white, opaque solid product within about 30 seconds which could be demolded within about 50 seconds.

COMPARATIVE EXAMPLE 6A To demonstrate that initiator compounds having a functionality of 3 but which have not been reacted with an alkylene oxide cannot be employed as the polyol to produce the compositions of the present invention, Example 6 was duplicated by substituting glycerine and again substituting trimethylol propane as the polyol component, i.e., as a replacement for the glyceineethylene oxide reaction product.

In both instances, the formulations did not demonstrate an instant set capability and they could not be demolded within 10 minutes after casting. After several hours, these castings were found to be low strength foams.

EXAMPLES OF VARIOUS LIQUID POLYOXYALKYLENE MODIFIER COMPOUNDS EXAMPLE 7 Same procedure as in Example 1A employing the following composition. 33 grams of Voranol CP-260 33 grams of the reaction product of allyl alcohol with a 50-50 wt. mixture of propylene oxide and ethylene oxide having a molecular weight of about 1,800

and finally end capped with a methyl group, as the liquid modifier. 33 grams of Hylene TM 1 cc of lead octoate 24% Pb).

The mixture set into a rigid, hard, white, opaque solid having a density of about 1.12 grams/cc within about seconds which could be demolded within about 40 seconds.

EXAMPLE 8 Same procedure as in Example 1A employing the following composition. 33 grams of Voranol CP-260 33 grams of the adduct of propylene oxide onto butanol and having a molecular weight of about 2,000. 33 grams of Hylene TM 1 cc of lead octoate (24% Pb).

The mixture set into a rigid, white, opaque, solid product within about 20 seconds which could be demolded within about 40 seconds.

EXAMPLE 9 Same procedure as in Example 1A employing the fol- EXAMPLE 10 EXAMPLE 1 1 Same procedure as in Example 1A employing the following composition. 30 grams of Voranol CP-260 30 grams of Voranol CP-470l (the reaction product of glycerine with propylene oxide end-capped with ethylene oxide and having an average molecular weight of about 4,700) 30 grams of Hylene TM 1 cc lead octoate The mixture instantly set into a rigid, transparent, solid product within about 20 seconds and could be demolded within about 30 seconds. The casting had a density of 1.1 grams/cc.

EXAMPLES OF VARIOUS POLYISOCYANATES, POLYOLS AND MODIFIER COMPOUNDS EXAMPLE 12 Same procedure as in Example 1A employing the following composition. 33 grams of Voranol CP-260 33 grams of Voranol CP-3000 (glycerine initiated polyoxypropylene glycol having an average molecular weight of about 3,000) SO'grams Isonate [43L 1 cc T-9 catalyst (stannous octoate commercially available from Metal and Thermit Corp.). The mixture rapidly set into a rigid, transparent, solid within about 15 seconds and could be demolded within about 30 seconds.

EXAMPLE 1 3 Same procedure as in Example lA employing the following composition. 30 grams of Voranol CP-260 30 grams of Voranol CP- 1 500 (glycerine initiated polyoxypropylene glycol having an average molecular weight of about 1,500) 30 grams of Hylene TM 1 cc of T-9 catalyst The mixture instantly set into a transparent, solid product within about 40 seconds and could be demolded within about 60 seconds.

COMPARATIVE EXAMPLE l3-A Same procedure as in Example lA employing the following composition.

30 grams of Voranol CP-260 30 grams of Voranol CP-700 (glycerine initiated polyoxypropyleneglycol having an average molecular weight of about 700) 30 grams of Hylene TM 1 cc T-9 catalyst The mixture demonstrated instant set characteristics but the product swelled and cracked.

EXAMPLE 14 Same procedure as in Example lA employing the following composition. 30 grams of Voranol CP-26O 31 grams of a triol prepared by reacting glycerine with a mixture of propylene oxide and ethylene oxide having an average molecular weight of about 4100 and about 16 weight percent ethylene oxide). 30 grams Hylene TM 1 cc lead octoate (24% lead) The mixture instantly set within about 30 seconds and the rigid, solid, clear casting was demolded within about 50 seconds.

EXAMPLE 15 Same procedure as in Example 1A employing the following composition.

30 grams of the reaction product of glycerine with propylene oxide in a molar ratio of about 1:3 respectively.

30 grams voranol CP-4701 (glycerine initiated polyoxypropylene glycol end-capped with ethylene oxlde) 45 grams Hylene W 1 cc lead octoate (24% Pb) At the end of 180 seconds the mixture was still liquid; at 195 seconds the mixture began to gel rapidly, and at 210 seconds the casting was a rigid transparent tackfree solid.

When the same formulation was catalyzed by cc of 24% Pb octoate, the solidification was not greatly accelerated, e.g., the mix was still liquid at 120 seconds, gelling occurred rapidly at 135 seconds, and the product was a transparent rigid solid at 150 seconds after catalyst addition.

EXAMPLE 16 Same procedure as in Example 1A employing the following composition.

30 grams of the reaction product of glycerine with propylene oxide at a molar ratio of 1:3 respectively.

30 grams of Voranol CP-470l 30 grams of hexamethylene diisocyanate 1 cc of lead octoate (24% Pb) The mixture set into a transparent, rigid, solid within about 70 seconds and could be demolded within about 90 seconds.

EXAMPLE 17 Same procedure as in Example 1A employing the following composition.

26 grams of Voranol CP-450 (glycerine initiated polyoxypropylene glycol having an average molecular weight of about 450).

grams of Voranol CP-4701 16 grams of xylylene diisocyanate 0.7 cc of lead octoate 24% Pb) The mixture instantly set into a transparent, rigid, solid product within about 30 seconds which could be demolded within about 50 seconds.

EXAMPLE 18 Same procedure as in Example 1A employing the following composition.

16 33 grams of Voranol CP-260 33 grams of a butanol initiated polyoxypropylene glycol having an average molecular weight of about 1000. 33 grams of Hylene TM 1 cc of lead octoate catalyst The mixture instantly set into a transparent, rigid, dense product within about 20 seconds and could be demolded within about 35 seconds.

EXAMPLE 19 EXAMPLE 20 Same procedure as in Example 1A employing the following components: 35 grams of Voranol CP260 30 grams of distilled tall oil 35 grams of Hylene TM 1 cc of stannous octoate (T-9) About 30 seconds after catalyst addition, the liquid reactants suddenly solidified into an opaque, off-white, rigid, solid having a density of 1.15 grams/cc.

' EXAMPLE 2 l 33 grams of Voranol CP-260 30 grams of distilled Tall oil 45 grams of PAH (polymethylenepolyphenylisocyanate having an average functionality of about 2.6 and an NCO equivalent weight of about 133) I 1 cc T-9 catalyst About 35 seconds after catalyst addition, the mixture suddenly froze into a rigid, solid material having a density of 1.04 grams/cc.

EXAMPLE 22 Same procedure as in Example 1A employing the following components:

30 grams of the reaction product of pentaerythritol with propylene oxide in a molar ratio of l to 5 respectively.

30 grams of linseed oil 30 grams of toluene diisocyanate 1 cc of T-9 catalyst The mixture suddenly set into a dense, solid product.

EXAMPLE 23 Same procedure as in Example 1A employing the following components:

33 grams of the reaction product of pentaerythritol with propylene oxide in a molar ratio of l to 5 respectively.

30 grams of distilled tall oil 33 grams of toluene diisocyanate 1 cc of T-9 catalyst The mixture solidified within about 30 seconds after catalyst addition and was demolded after about 45 seconds after catalyst addition. The rigid, solid casting had a density of 1.11 grams/cc.

EXAMPLE 24 Same procedure as in Example 1A employing the following components: 30 grams of Voranol CP-260 20 grams of oleic acid 46 grams of PAPI (polymethylene polyphenylisocyanate) 1 cc of T-9 catalyst About 35 seconds after catalyst addition, the mixture suddenly set into a rigid, light brown casting which had a density of about 1.04 grams/cc.

EXAMPLE 25 grams/cc.

EXAMPLE 26 Same procedure as in Example 1A employing the fol lowing components: 30 grams of the reaction product of glycerine with propylene oxide to a molecular weight of about 260. 20 grams of castor oil 46 grams of PAP! 1 cc of T-9 catalyst About 25 seconds after catalyst addition, the mixture set into a rigid, solid which was demolded in about 1 minute after catalyst addition. The casting had a density of 1.12 grams/cc.

EXAMPLE 27 Same procedure as in Example 1A employing the following components: 30 grams of Voranol CP-260 30 grams of Hylene TM 30 grams of l,2,3,4-tetrahydronaphthalene 1 cc of lead octoate (24% Pb) About 15 seconds after catalyst addition, the mixture suddenly set into a rigid, clear, transparent, solid.

EXAMPLE 28 Same procedure as in Example 1A employing the following components: 30 grams of the reaction product of glycerine with propylene oxide at a mole ratio of about 1 to 3 re-- Density l gram/cc Shore D Hardness about )2 EXAMPLE 29 Same procedure as in Example 1A employing the following components: 30 grams reaction product of glycerine with propylene oxide to a molecular weight of about 260. 30 grams of l,2,4-trichlorobenzene 30 grams toluenediisocyanate 1 cc lead octoate About 15 seconds after catalyst addition, the mixture suddenly set into a rigid, transparent solid.

EXAMPLE 30 Same procedure as in Example 1A employing the following components: 35 grams of the reaction product of glycerine with propylene oxide to a molecular weight of about 260. 20 grams of l,2,3,4-tetrahydronaphthalene 10 grams of l,2,4-trichlorobenzene 35 grams of toluene diisocyanate 0.3 cc of lead octoate The mixture suddenly set into a rigid, transparent solid.

EXAMPLE 31 Same procedure as in Example 1A employing the following components: 30 grams of the reaction product of glycerine with propylene oxide to a molecular weight of about 260. 30 grams of a-chloronaphthalene 30 grams of toluenediisocyanate 0.4 cc of lead octoate About 20 seconds after catalyst addition, the mixture suddenly set into a rigid, transparent solid.

EXAMPLE 32 A. Same procedure as in Example 1A employing the following components: 30 grams of the reaction product of glycerine with propylene oxide to a molecular weight of about 260. 30 grams of l,2,4-triethylbenzene (b.p. approx. 215C) 30 grams of toluenediisocyanate 0.4 cc of lead octoate About 30 seconds after catalyst addition, the mixture suddenly set into a rigid, opaque solid. About 45 seconds after catalyst addition, the casting was demolded and had a density of 1.12 grams/cc.

B. Comparative Example Use of Modifier Compound With a Boiling Point Below About C Same procedure as in Example 1A employing the following components: 30 grams of the reaction product of glycerine with propylene oxide to a molecular weight of about 260. 30 grams of ethylbenzene (b.p. approx. 136C) 30 grams of toluene diisocyanate 0.4 cc of lead octoate About 20 seconds after catalyst addition, the mixture suddenly swelled with gross bubble formation to yield an expanded rigid casting having an apparent density of 0.67 grams/cc.

EXAMPLE 33 Same procedure as in Example l-A employing the 'following composition:

30 grams of the reaction product of glycerine with about 3 moles of ethylene oxide per mole of glycerme. 32 grams xylylene diisocyanate 30 grams tris( 2-chloroethyl)phosphate 0.5 cc lead octoate The mixture instantaneously set within about seconds after catalyst addition and was demolded within about 30 seconds after catalyst addition thereby producing a clear, transparent, rigid, non-brittle solid casting having a density of about 1.25 grams/cc.

EXAMPLE 34 Same procedure as in Example l-A employing the following composition:

30 grams of the reaction product of glycerine with 3 moles of propylene oxide per mole of glycerine having a hydroxyl equivalent weight of about 87.

46 grams PAPI (polymethylene polyphenylisocyanate) grams tri-n-butylphosphate 1 cc stannous octoate catalyst The mixture suddenly solidified within about 20 seconds after catalyst addition and the resultant casting was demolded within about 30 seconds after catalyst addition. The product was a tough, dark colored (transparent in very thin sections) solid, rigid product having a density of 1.15 grams/cc.

EXAMPLE 35 Same procedure as in Example 1A employing the following composition. 30 grams Voranol CP-260 30 grams toluenediisocyanate 30 grams tricresyl phosphate 0.5 cc lead octoate (24% lead) The mixture was cast as a sheet and within about 10 seconds after catalyst addition, suddenly solidified into a tough, colorless, transparent rigid solid.

EXAMPLE 36 Same procedure as in Example 1A employing the following composition: 30 grams of the reaction product of glycerine with propylene oxide in a molar ratio of about 1:3 having a hydroxyl equivalent weight of 87. 30 grams of toluene diisocyanate 30 grams of triethylphosphate 0.5 cc. of lead octoate The mixture was cast as a sheet which instantly set into a transparent, relatively soft sheet having an elongation less than about 100 percent. The relative softness of this product is believed to have been derived from a side effect of the triethylphosphate also functioning as a plasticizer at this concentration.

EXAMPLE 37 Same procedure as in Example 1A employing the following composition. 30 grams of Voranol CP-260 30 grams of toluene diisocyanate 30 grams of tributylphosphite 0.5 cc of lead octoate The mixture suddenly solidified into an opaque, white, rigid casting within about 10 seconds after catalyst addition.

EXAMPLE 38 Same procedure as in Example 1A employing the following composition.

30 grams of Voranol CP-26O 30 grams of toluene diisocyanate 30 grams of bis(2-bromopropyl)2-bromopropane phosphonate 1 cc of stannous octoate (T-9) The mixture suddenly solidified into a transparent, solid, rigid casting within about 20 seconds after catalyst addition and was demolded within about 40 seconds after catalyst addition.

EXAMPLE 39 Same procedure as in Example 1A employing the following composition. 45 grams of Voranol CP-260 30 grams of tris(2-chloroethyl)phosphate grams of lSONATE 143L (a diphenylmethane diisocyanate which has been dimerized with phosphoric acid and having an NCO equivalent weight of about 144 and an average functionality of about 2.25) 1 cc of dibutyl tin dilaurate The above mixture was cast onto a Mylar sheet and suddenly solidified within about 20 seconds after catalyst addition and within about 40 seconds after catalyst addition a rigid, yellow-brown, transparent sheet was removed from the casting surface.

Test specimens cut from the above prepared sheet had the following properties.

tensile strength (ultimate) 7500 psi elongation l0 Hardness, Shore D 90 EXAMPLE 40 Same procedure as in Example l-A employing the following composition:

30 grams of the reaction product of glycerine with ethylene oxide in a molar ratio of 1:3 having a hydroxyl weight of 75.9.

30 grams of propylene carbonate 30 grams of toluene diisocyanate 2,4- and 20% 2,6-isomer mixture) 0.5 cc of lead octoate The mixture instantly set within about 10 seconds after catalyst addition into rigid, transparent casting having a density greater than 1 gram/cc.

EXAMPLE 41 Same procedure as in Example l-A employing the following composition: 30 grams of Voranol CP-260 20 grams of bis( 2-chloroethyl)carbonate 20 grams of toluene diisocyanate 0.5 cc of stannous octoate The mixture suddenly solidified within about 10 seconds after catalyst addition which was demolded within about 20 seconds after catalyst addition thereby producing a transparent, rigid dense casting.

EXAMPLE 42 Same procedure as in Example l-A employing the following composition: 45 grams of Voranol CP-260 30 grams of propylene carbonate 69 grams of polymethylene polyphenylisocyanate 1 cc of stannous octoate The above mixture was cast onto a Mylar sheet which instantly set within about 20 seconds after catalyst addition.

The dark brown, rigid, transparent product was removed from the Mylar casting surface within about 45 seconds after catalyst addition. The productwas found to possess the following properties.

tensile strength 4940 psi elongation l 2% Hardness, Shore D EXAMPLE 43 Same procedure as in Example l-A employing the following composition:

30 grams of the reaction product of glycerine with eth ylene oxide in a molar ratio of 1:3 respectively having a hydroxyl equivalent weight of about 75.9.

32 grams of xylene diisocyanate 30 grams of the cyclic tetramer of ethylene oxide 0.5 cc of lead octoate (24% Pb) The mixture suddenly solidified within about secands after catalyst addition and the casting was demolded within about 25 seconds after catalyst addition. The casting was a transparent rigid solid which had a density of 1.2 grams/cc.

EXAMPLE 44 Same procedure as in Example l-A employing the following composition 30 grams of Voranol CP-26O 30 grams of toluene diisocyanate 30 grams of mixture of cyclic polyethers of propylene oxide containing pentamer and higher homologs.

1 cc of lead octoate.

The mixture suddenly solidified within about 12 seconds after catalyst addition and the solid product was demolded within about 30 seconds after catalyst addition yielding a translucent, rigid off-white casting having a density of 1.15 grams/cc.

EXAMPLE 45 EXAMPLE 46 Same procedure as in Example l-A employing the following composition:

32 grams of Voranol CP-260 32 grams of toluene diisocyanate (80/20 mixture of 2,4- and 2,6-isomers) 3 grams of Chlorowax No. 40 (a liquid chlorinated paraffin having a specific gravity of 1.15, a viscosity of 25 poises at 25C, manufactured and sold by Diamond-Shamrock Chemicals) 0.5 cc of lead octoate The mas suddenly set, within about 10 seconds after catalyst addition, into a rigid casting having a density of 1.2 grams/cc and had no visual indications of cracks, distortions or bubble formation.

EXAMPLE 47 Same procedure as in Example l-A employing the following composition:

30 grams of Voranol CP-260 25 grams of 1,2,3-trichloropropane 45 grams of PAH (a polymethylene polyphenyl isocyanate having an average functionality of about 2.6-2.8 and NCO equivalent weight of about I34).

1 cc of stannous octoate (T-9 commercially available from M 8L T Chemicals).

The mixture suddenly solidified within about 30 seconds after catalyst addition and 15 seconds later was demolded. The dark, dense, rigid casting had a density of 1.2 g/cc.

EXAMPLE 48 Same procedure as in Example l-A employing the following composition: 30 grams of Voranol CP-260 30 grams of toluene diisocyanate (/20 mixture of 2,4- and 2,6-isomers) 0.5 cc of lead octoate (24% lead) 20 grams tetrabromoethane The blend suddenly solidified within about 15 seconds after catalyst addition and was demolded within about 30 seconds after catalyst addition thereby producing a dense, rigid, bubble-free casting having a density of 1.58 grams/cc.

EXAMPLE 49 Same procedure as in Example l-A employing the following composition. 37 grams of Voranol CP-260 37 grams of toluene diisocyanate (80/20 blend of 2,4-

and 2,6-isomers) 3 grams of tetrabromoethane 0.5 cc of lead octoate (24% lead) The mixture suddenly set within about 15 seconds 'after catalyst addition to yield a dense rigid, bubblefree casting.

EXAMPLE 50 Same procedure as in Example l-A employing the following composition. 30 grams of Voranol CP-260 30 grams of TDI (80/20 mixture of 2,4- and 2,6-

isomers) 25 grams of 1,10-dribromodecane 0.5 cc of lead octoate The mixture suddenly solidified within about 15 sec-' onds after catalyst addition and was demolded within about 30 seconds after catalyst addition to provide a dense, rigid, bubbleand crack-free casting having a density of 1.35 grams/cc.

EXAMPLE 51 Same procedure as in Example l-A employing the following composition.

30 grams of Voranol CP-26O 30 grams of toluene diisocyanate (80/20 mixture of 2,4- and 2,6-isomers) 30 grams of bromoform 0.5 cc of lead octoate I The mixture solidified within about 15 seconds providing a dense, rigid, bubble-free casting.

EXAMPLE 52 Same procedure as in Example l-A employing the following composition. 30 grams of Voranol CP-260 30 grams of hexachlorobutadiene 30 grams of toluene diisocyanate (80/20 mixture of 2,4- and 2,6-isomers) 1 cc of lead octoate The mixture solidified to within 15 seconds after catalyst addition to provide a dense, rigid, bubbld-free casting.

EXAMPLE 53 Same procedure as in Example l-A employing the following composition. 32 grams of Voranol CP-260 32 grams of toluenediisocyanate (80/20 mixture of 2,4-

and 2,6-isomers) 4 grams of polyepichlorohydrin diol* having a molecular weight of about 2,000 0.5 cc of lead octoate The polyepichlorohydrin diol was prepared by slowly adding over a period of about 1 hour 17 pounds of epichlorohydrin to a mixture containing 15 pounds of benzene, 400 grams of 48% aqueous fluoroboric acid and 503 grams of water. The epichlorohydrin addition was conducted at 47C and digested for about 30 minutes at 47C; 40 pounds of benzene was added and 155 pounds of epichlorohydrin was added over a 5 V4 hour period and digested at 47C for about 30 minutes. The water was removed via a water-benzene azeotrope at 90C for 2 hours after neutralizing the catalyst with 5 V4 pounds of 4% aqueous NaOH. The benzene-polyepichlorohydrin mixture was filtered and the benzene removed at 90C at reduced pressure in about 2 hours. The prod uct contained 1.72% 0H by analysis.

This mixture rapidly set into a dense, rigid casting having a density of 1.2 grams/cc.

EXAMPLE 54 Same procedure as in Example l-A employing the following composition: 40 grams of Voranol CP-260 40 grams of toluene diisocyanate (80/20 mixture of 2,4- and 2,6-isomers) 40 grams of Chlorowax 40 0.5 cc of lead octoate The mixture rapidly solidified thereby forming a dense, rigid casting having a density greater than 1 gram/cc.

EXAMPLE 55 (COMPARATIVE) This comparative example illustrates the inoperability of halogenated aliphatic compounds having a boiling point below 150C. Same procedure as in Example l-A employing the following composition:

30 grams of Voranol CP-260 30 grams of perchloroethylene (boiling point 121C) 30 grams of toluenediisocyanate (80/20 mixture of 2,4-

and 2,6-isomers) 0.8 cc of lead octoate The above mixture suddenly expanded within about seconds after catalyst addition into a non-uniform cellular rigid mass having a density of 0.48 gram/cc.

24 EXAMPLE 56 Same procedure as in Example l-A employing the following composition:

30 grams of Voranol CP-260 30 grams of toluene diisocyanate (/20 mixture of 2,4- and 2,6-isomers) 40 grams of a-chloronaphthalene 0.05 cc of lead octoate (24% lead) The mixture suddenly solidified about 65 seconds after catalyst addition to yield a transparent rigid polymer which was demolded about seconds after catalyst addition. The density of this casting was found to be 1.17 grams/cc.

EXAMPLE 57 Same procedure as in Example l-A employing the following composition:

30 grams of Voranol CP-260 30 grams of toluene diisocyanate 80/20 mixture) 15 grams of Voranol CP-l500 15 grams of triethylbenzene 0.05 cc of lead octoate (24% lead) This blend was cast into a polyethylene mold and the blend suddenly solidified about 50 seconds after catalyst addition and was removed from the mold 75 seconds after catalyst addition. This transparent rigid casting was found to have a density of 1.16 grams/cc.

EXAMPLE 58 EXAMPLE 59 Same procedure as in Example l-A employing the following composition:

60 grams of Voranol RS-350 30 grams of toluene diisocyanate (80/20 mixture) 30 grams of trichlorobenzene 1 cc of lead octoate (24% lead) This blend was cast into a polyethylene mold and was found to solidify about 15 seconds after catalyst addition; the casting was removed from the mold 25 seconds after catalyst addition.

EXAMPLE 60 Same procedure as in Example l-A employing the following composition: grams of Voranol CP-260- 130 grams of toluenediisocyanate (80/20 mixture) 20 grams of Chlorowax No. 40 0.5 cc of lead octoate (24% lead) This blend was cast into a Mylar tray and was found to solidify and be removed from the Mylar tray as a dense rigid sheet in less than 60 seconds after catalyst addition. Appropriate tensile bars were cut from this cast resin and were found to exhibit an ultimate tensile of 15,600 psi at elongation.

EXAMPLE 61 ify 20 seconds after catalyst addition. The rigid castingwas demolded 40 seconds after catalyst addition and was found to have a density of 1.10 grams/cc.

EXAMPLE 62 Same procedure as in Example l-A employing the following composition:

300 grams of the reaction product of glycerine with 3 moles of propylene oxide per mole of glycerine.

400 grams of a prepolymer prepared from the reaction product of 3 moles of propylene oxide per mole of glycerine and toluene diisocyanate, said prepolymer containing 31% NCO.

300 grams of trichlorobenzene 1 cc of lead octoate (24% Pb) This liquid blend was cast between 2 parallel sheets of polyethylene; the liquid mix was found to solidify in less than 1 minute after catalyst addition and the cast product was removed from the mold in less than 2 minutes after catalyst addition. This casting was found to be transparent and bubble-free.

EXAMPLE 63 Same procedure as in Example 1-A employing the following composition: 60 grams of Voranol RS-350 30 grams of toluene diisocyanate (80/20 mixture) 20 grams of 3-methylsulfolane 1 cc of lead octoate 24% Pb) This liquid blend solidified in less than 30 seconds and was demolded about 30 seconds later to yield a hard, transparent, rigid casting.

EXAMPLE 64 A. Example of the present invention.

Same procedure as in Example l-A employing the following composition:

45 grams of Voranol CP-260 (OH equivalent wt.

approx. 87)

45 grams of Hylene TM 30 grams of Voranol CP-4701 0.4 cc of lead octoate 24% Pb) This blend was cast into a Mylar tray and was found to solidify into a transparent sheet in less than a minute after catalyst addition. This sheet was removed from the mold in less than 2 minutes after catalyst addition and had physical properties as indicated in the table below.

B. Comparative Same procedure as in Example l-A employing the following composition:

105 grams of Voranol CP-700 (OH equivalent wt.

approx. 232) 30 grams oi Hylene TM 40 grams of Voranol CP-4701 1 cc of lead octoate 24% Pb) This blend was also cast into a Mylar tray and was found to solidify 35 seconds after catalyst addition. The

weak, rubbery transparent cast sheet was removed from the mold about 20 seconds after catalyst addition and had properties as indicated in the table below, which shows that polyols employed as component A having an OH equivalent weight above 230 do not pro duce the products of the present invention, i.e., the elongation was greater than Ultimate Polymer Tensile Elongation Hardness A (present invention) 6540 psi 20% Shore D (comparative) 104 psi 92% 45 Shore A The following examples demonstrates the use of byproduct streams containing mixtures of aromaticcontaining compounds.

EXAMPLE 65 Same procedure as in Example l-A employing the following composition:

30 grams of the reaction product of glycerine with propylene oxide in a molar ratio of 1:3 respectively, said product having a molecular weight of about 260.

30 grams of a mixed stream of aromatic-containing compounds as the residue stream obtained from the manufacture of ethyl benzene and having a typical composition by weight as follows:

3% triethylbenzene 1 1% tetraethylbenzene 1% pentaethylbenzene 3% bis-ethylphenylethane 8% ethylphenyl-phenylethane 13% l,l-diphenylethane 61% higher boiling components 30 grams of toluenediisocyanate (80/20 mixture of 2,4-

and 2,6-isomers) 1 cc of stannous octoate T-9 (M and T Chemicals) The blend was cast into a polyethylene mold and suddenly solidified within 20 seconds after catalyst addition. The rigid, dense casting was demolded within 60 seconds after catalyst addition.

EXAMPLE 66 A. Present Invention Same procedure as in Example l-A employing the following composition: 60 grams of Voranol RS-35O 30 grams of toluene diisocyanate 60 grams of Voranol CP-3000 0.5 cc. of lead octoate (24% Pb) The mixture was cast as a sheet in a Mylar tray and allowed to cure overnight at room temperature.

B. Prior Art Comparison Same procedure as in Example l-A employing the following composition: 60 grams of Voranol RS-350 30 grams of toluenediisocyanate 60 grams of dioctylphthalate 0.5 cc of lead octoate (24% Pb) The mixture was cast as a sheet in a Mylar tray and allowed to cure overnight at room temperature.

C. After curing overnight, each of the panels from A and B above were sprayed with Krylon black enamel in 2 inch wide stripes. After 2 hours of drying at room temperature, the paint coating was found to be poorly attached to panel B, an example of the prior art, but was well attached to panel A, an example of the present invention.

D. Another portion of each of panels A and B were sprayed with 2 inch wide stripes of Illinois Bronze- Powder and Paint Co.s Flat Black No. 607. The paint dried within an hour on Panel A, the present invention, whereas on Panel B, the prior art, the panel was still tacky after 6 hours.

After 72 hours of drying at room temperature, a fingernail scratch removed paint from panel B, the prior art panel; whereas panel A, the present invention, resisted removal of paint by fingernail scratching. A finger pressure dry rag wipe also removed paint from panel B, the prior art; whereas no paint was removed by this test from panel A, the present invention.

Some amine type catalysts will catalyze the urethane reaction to produce instant set products, but the resultant products are of low density, i.e., less than about I gram/cc and contain many bubbles which adversely affect the physical properties. This inoperability of the amine type catalysts insofar as the present invention is concerned is demonstrated by the following comparative Example 67.

EXAMPLE 67 (COMPARATIVE) A. Same procedure as in Example 1A employing the following composition.

30 grams of Voran 3O gra hylenetriamine in di- *bout 90 seconds to olymer containing y of 0.6 grams/cc. ,dth difficulty within B. Same procedure as in Example 1A employing the following composition: 30 grams of Voranol CP-260 30 grams of Voranol CP-3000 30 grams of Hylene TM 2 cc of triethylamine The mixture slowly set within about 60 seconds which could be demolded with difficulty within about 90 seconds. The product was an opaque, rigid solid EXAMPLE 68 (COMPARATIVE) Three rigid castings were prepared by the procedure of Example l-A employing the following formulations.

Formulation A (Present Invention) 30 grams of the reaction product of glycerine with propylene oxide in a molar ratio of about 1:3 respectively 30 grams of toluene diisocyanate 30 grams of Voranol P-4000 1 cc of lead octoate (24% Pb) Formulation B (Present Invention) 30 grams of the reaction product of glycerine and propylene oxide at a molar ratio of about 1:3 respectively 30 grams of toluene diisocyanate 20 grams of trichlorobenzene 0.2 cc of lead octoate Formulation C (Prior Art Teachings US. Pat. No. 3,378,51 1) 30 grams of the reaction product of glycerine and propylene oxide in a molar ratio of about 1:3 respectively 30 grams of toluene diisocyanate 30 grams of diisodecyl phthalate 1 cc of lead octoate (24% Pb) Each of the above formulations A, B and C suddenly solidified into a dense, rigid casting within about 30 seconds after catalyst addition and were demolded within about seconds.

Several A inch X %inch X 1% inches specimens were cut from the castings of Formulations A, B, and C and immersed in various solvents at room temperature. Periodic observations were taken to ascertain the condition of each specimen after exposure to the solvents. The solvents and observations are given in the following Table.

OBSERVATION SOLVENT Formulation A Formulation B Formulation C Acetone no change after no change severe cracks 1 hr. exposure after I hr. developed after exposure I hr. exposure Tetrahydrofuran slight trace not tested severe cracking of cracking and swelling after I hr.

exposure Methylene chloride slight trace no change severe cracking of cracking after 1 hr. with particles after 1 hr. exposure separating exposure from specimen after 1 hr. 8 exposure. Ethylene dichloride intact after no change developed severe 36 hours of after 5 hrs. cracks after exposure of exposure 5 hrs. of exp.,

Continued OBSERVATION SOLVENT Formulation A Formulation B Formulation C total disintegration into discrete particles after 36 hrs. exp. Ethyl Acetate no change no change slight decrepiafter 36 hrs. after 7 hrs. tation into of exposure of exposure discrete particles after 7 hrs. and total disintegration after 36 hrs.

, exposure. Methylisobutyl no change after slight swelling ketone 36 hrs. of not after 36 hrs. exposure tested of exposure.

The preceding example clearly demonstrates the superior solvent resistance of the composition of the present invention, formulationA and B, as compared to the prior art, US. Pat. No. 3,378,511, formulation C.

EXAMPLE 69 moved from the mold. The cast object, pipe plug, had

a density greater than 1 gram/cc.

EXAMPLE 70 A 3 /2 inches diameter spur gear was removed from a gear box having a gear and pinion arrangement and an elastomeric silicone mold of said spur gear was prepared.

Employing the procedure of Example l-A, the following composition was poured into the mold. 60 grams of Voranol CP-260 60 grams of toluene diisocyanate 30 grams of tetrahydronaphthalene 0.2 cc of lead naphthenate (24% Pb) Within about 25 seconds after catalyst addition, the composition suddenly solidified and a rigid polyurethane spur gear was removed from the mold after the lapse of an additional 45 seconds. The gear had a density of greater than 1 gram/cc.

EXAMPLE 71 Preparation of Decorative Article A sheet of polyethylene was vacuum formed over a half relief sculptured horse s head to yield a thin walled polyethylene mold of said horses head.

The following non-flexible urethane composition prepared by the procedure of Example l-A was poured into the mold:

45 grams of Voranol CP-260 72 grams of an isocyanate terminated prepolymer prepared from toluene diisocyanate and tetrabromobisphenol A, said prepolymer having an NCO content of 30 grams of triethylbenzene 1 cc of lead octoate catalyst.

The composition suddenly solidified in about 20 seconds after catalyst addition and within about seconds after catalyst addition a rigid polyurethane replica of the horse head having a density greater than 1 gram/cc was removed from the mold.

EXAMPLE 72 In each of the following experiments, all of the components except the catalyst were blended together and then the catalyst was added and blended. The resultant mixture was then poured into a 250 cc polyethylene beaker.

The compositions and results are given in the follow ing table. The times were measured from the instant the catalyst was added.

Continued EXPERIMENT EXPERIMENT EXPERIMENT A B C N.D. not detcrmined. "Composition was still liquid after 300 seconds. "Composition was still liquid after 720 seconds.

The polyol employed was the reaction product of glycerinc with propylene oxide to an equivalent weight of about 87.

f] an 80/20 mixture of l-l-llo-toluene'diisocyanate having an NCO equivalent weight of about 87.

"ATE acetylene tetrahromide.

NMM N-methylmorpholine.

"TEDA a 33% solution ot'triethylenediamine in diprupyleneglyeol.

PBO lead octoate containing 24% Ph.

EXAMPLE 73 In each of the following experiments, all of the components except the catalyst were blended together and then the catalyst was added and blended. The resultant mixture was then poured into a 250 cc polyethylene beaker.

In each of the follmving'experiments, the polyol employed was the reaction product of glycerine with propylene oxide to an equivalent weight of about 87.

In each of the following experiments, the polyisocyanate employed was an 80/20 mixture of 2,442,6- toluene diisocyanate (TDI) having an NCO equivalent weight of about 87.

In each of the following experiments acetylene tetrabromide (ATB) was employed as the modifier.

In each of the following experiments. the catalysts employed and their designations are as follows:

DBTDL dibutyl tin dilaurate CdOc cadmium octoate CoOc I part cobalt octoate dissolved in 2 parts triethyl benzene ZN zinc naphthenate SbOc antimony octoate PMP 1 part phenyl mercuric propionate in 1 part of propylene carbonate.

The compositions and results of the experiments are given in the following table.

260, said prepolymer having an NCO content of about 30% by weight,

20 grams of ethylene carbonate.

1 cc of lead octoate (24% lead by weight).

The mixture suddenlysolidified within about 30 seconds and was demolded within about 60 seconds after catalyst addition. The solid, rigid cast sheet had a density of about 1 g/cc and a Shore D hardness of about 85.

EXAMPLE 75 Same procedure as in Example 74 with the following components: 50 grams of an adduct of pentaerythritol with ethylene oxide having an OH equivalent weight of about 86, 50 grams of an -80/20 mixture of 2,4-/2,6-toluene diisoeyanate having an NCO equivalent weight of about 8%, 30 grams of a 50/50 mixture by weight of ethylene carbonate and propylene carbonate, 1 cc of antimony octoate. v The mixture suddenly solidified within about 30 seconds and was demolded within about 90 seconds after catalyst addition. The solid. rigid cast sheet had a density of about g/cc and a Shore D hardness of about 70.

EXPERIMENT NO.

Polyol. grams 33 33 33 33 33 33 TDI, grams 33 33 33 33 33 33 ATB, grams 2O 20 20 20 20 DBTDL, cc 0.5 CdOc, cc 0.5 CoOc. cc 0.5 ZN. cc 0.5 SbOc, cc 0.5 PMP. cc 0.5 Time for solidification, sec. 20 20 40 30 Time* solid casting was removed from the mold, sec. 40 6O 60 I20 90 60 Density, g/cc 1.3 L3 1.3 1.3 1.3 1.3

The times were measured from the instant the catalyst was added.

We claim:

EXAMPLE 74 The procedure of Example l-A was employed, except that the mixture was poured into a Mylar tray, with the following components:

grams of an adduct of glycerine and 1,2-propylene oxide having an average molecular weight of about 260.

75 grams of a prepolymer prepared by reacting an excess of an 80/20 mixture of 2,4-/2.6-toluene diisocyanate with an adduct of glycerine and 1,2-propylene oxide having an average molecular weight of about A. a polyether polyol having from 3 to about 8 hy-- droxyl groups and a hydroxyl equivalent weight between about and about 230,

B. an organic polyisocyanate,

C. a liquid modifier compound having a boiling point above about C selected from the group consisting of organic carbonates and mixtures thereof, and

D. a non-amine-containing catalyst for urethane formation, which is an organo metal compound;

wherein components (A) and (B) are present in amounts so as to provide an NCOzOH ratio of from about 0.8:1 to about 2:1, component (C) is present in quantities of from about to about 50 percent with the proviso that when component (B) is an NCO- containing prepolymer containing less than about 40% NCO by weight, component (C) is employed in quantities of from about 10% to about 50% by weight of the sum of components (A), (B) and (C); and component (D) is present in quantities of from about 0.01 to about 10 percent by weight of the sum of the weights of components (A). (B) and (C); and wherein said polymer can be demolded within less than about 5 minutes, without the application of an external source of heat. after admixture of said composition.

2. The composition of claim 1 wherein components (A) and (B) are present in quantities such that the NCO:OH ratio of the (A) and (B) components is from about 0.95:] to about 1.111, component (C) is present in quantities of from about to about 50 percent by weight of the sum of components (A), (B) and (C) and wherein component (D) is present in quantities of from about 0.5 to about 3 percent by weight of the sum of the weights of components (A), (B) and (C).

3. The composition of claim 2 wherein component (D) is an organo-metal compound of a metal selected from tin, zinc, lead, mercury, cadmium, bismuth and antimony.

I 4. The composition of claim 3 wherein component (C) is a cyclic carbonate or mixture thereof.

5. The composition of claim 4 wherein component (C) is ethylene carbonate or propylene carbonate.

6. The composition of claim 5 wherein component (D) is an organo-tin compound or an organo-lead compound.

7. The composition of claim 3 wherein component (C) is an acyclic carbonate or mixture thereof.

8. The composition of claim 7 wherein component (C) is bis(2-chloroethyl)carbonate.

9. The composition of claim 8 wherein component (D) is an organo-tin compound or an organo-lead compound.

10. The composition of claim 1 wherein component (D) is employed in quantities of from about 0.05 to about 2 percent.

11. The composition of claim 1 wherein component (D) is employed in quantities of from about 0.1 to about 0.5 percent.

12. The articles resulting from casting the compositions of claim 1.

13. The articles of claim 12 wherein said articles are furniture components.

14. The articles of claim 12 wherein said articles are decorative objects.

15. The articles of claim 12 wherein said articles are machine components.

16. A process for producing solid, rigid, polyurethane articles having a density of at least 1 g/cc, a percent elongation of less than 80, and which can be demolded within aperiod of about 5 minutes without the addition of an external source of heat which process comprises:

1. admixing the components of a composition comprising A. a polyether polyol having from -3 to about 8 hydroxyl groups and a hydroxyl equivalent weight between about 75 and about 230,

B. an organic polyisocyanate,

C. a liquid modifier compound having a boiling point above about C selected from the group consisting of organic carbonates and mixtures thereof, and

D. a non-amine-containing catalyst for urethane formation, which is an organo metal compound;

wherein components (A) and (B) are present in amounts so as to provide an NCOzOH ratio of from about 0.811 to about 2:1 component (C) is present in quantities of from about 20 to about 50 percent with the proviso that when component (B) is an NCO-containing prepolymer containing less than about 40% NCO by weight, component (C) is employed in quantities of from about 10% to about 50% by weight of the sum of components (A), (B)

and (C); and component (D) is present in quantities of from about 0.01 to about 10 percent by weight of the sum of the weights of components (A), (B) and (C); and wherein said polymer can be demolded within less than about 5 minutes. without the application of an external source of heat. after admixture of said composition;

2. placing the admixed composition into a suitable mold wherein said composition solidifies within less than about 5 minutes to a solid having the aforesaid density and elongation; and

3. subsequently demolding the resultant article from the mold.

17. The process of claim 16 wherein components (A) and (B) are present in quantities such that the NCO- :OH ratio of the (A) and (B) components is from about 0.95:1 to about 1.1:1, component (C) is present in quantities of from about 30 to about 50 percent by weight of the sum of components (A), (B) and (C) and wherein component (D) is present in quantities of from about 0.5 to about 3 percent by weight of the sum of the weights of components (A), (B) and (C).

18. The process of claim 17 wherein component (D) is an organo-metal compound of a metal selected from tin, zinc. lead, mercury, cadmium. bismuth and antimony.

19. The process of claim 18 wherein component (C) is a cyclic carbonate or mixture thereof.

20. The process of claim 19 wherein component (C) is ethylene carbonate or propylene carbonate.

21. The process of claim 20 wherein component (D) is an organo-tin compound or an organo-lead compound.

22. The process of claim 18 wherein component (C) is an acyclic carbonate or mixture thereof.

23. The process of claim 22 wherein component (C) is bis(2-chloroethyl)carbonate.

24. The process of claim 23 wherein component (D) is an organo-tin compound or an organo-lead compound. I

25. The process of claim 16 wherein component (D) is employed in quantities of from about 0.05 to about 2 percent.

26. The process of claim 16 wherein component (D) is employed in quantities of from about 0.1 to about 0.5 percent.

27. The process of claim 16 wherein said mold is that of a furniture component.

28. The process of claim 16 wherein said mold is that of a decorative object.

29. The process of claim 16 wherein said mold is that of a machine component.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Q PATENT NO. 3,878,156

' DATED April 15, 1975 |NVENTOR(S) Franciszek Olstowski, et al.

it is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 3, line 25, "an" should be --as-.

Col. 5, line 12, "POLYESTER" should be --POLYETHER.

. Col. 6, line 51, insert a comma after "chlorophosphate" Col. 16, line 36-37 please add -Same procedure as in Example lA employing the following components:.

Col. 33, line 14, "0.01" should be -0.2. Q Claims 10 and 11, should be cancelled Col. 34, line 18, "0.01" should be -0.2.

Claims 25 and 26, should be cancelled.

0 Signed and Scaled this tenth Day of February 1976 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Atresrmg Ojfrcer Commissioner oj'Parenrs and Trademarks 

1. A NON-ELASTOMERIC, NON-CELLULAR, SOLID POLYMER HAVING A DENSITY OF AT LEAST ABOUT 1 GRAM/CC AND A PERCENT ELONGATION OF LESS THAN ABOUT 80 RESULTING FROM ADMIXTURE OF THE COMPONENTS OF A COMPOSITION COMPRISING: A. A POLYETHER POLYOL HAVING FROM 3 TO ABOUT 8 HYDROXYL GROUPS AND A HYDROXYL EQUIVALENT WEIGHT BETWEEN ABOUT 75 AND ABOUT 230, B. AN ORGANIC POLYISOCYANATE, C. A LIQUID MODIFIER COMPOUND HAVING A BOILING POINT ABOVE ABOUT 150*C SELECTED FROM THE GROUP CONSISTING OF ORGANIC CARBONATES AND MIXTURES THEREOF, AND D. A NON-AMINE-CONTAINING CATALYST FOR URETHANE FORMATION, WHICH IS AN ORGANO METAL COMPOUND; WHEREIN COMPONENTS (A) AND (B) ARE PRESENT IN AMOUNTS SO AS TO PROVIDE AN NCO:OH RATIO OF FROM ABOUT 0.8:1 TO ABOUT 2:1, COMPONENT (C) IS PRESENT IN QUANTITIES OF FROM ABOUT 20 TO ABOUT 50 PERCENT WITH THE PROVISO THAT WHEN COMPONENT (B) IS AN NCQ-CONTAINING PREPOLYMER CONTAINING LESS THAN ABOUT 40% NCO BY WEIGHT, COMPONENT (C) IS EMPLOYED IN QUANTITIES OF FROM ABOUT 10% TO ABOUT 50% BY WEIGHT OF THE SUM OF COMPONENTS (A), (B) AND (C); AND COMPONENT (D) IS PRESENT IN QUANTITIES OF FROM ABOUT 0.01 TO ABOUT 10 PERCENT BY WEIGHT OF THE SUM OF THE WEIGHTS OR COMPONENTS (A), (B) AND (C); AND WHEREIN SAID POLYMER CAN BE DEMOLDED WITHIN LESS THAN ABOUT 5 MINUTES, WITHOUT THE APPLICATION OF AN ESTERNAL SOURCE OF HEAT, AFTER ADMIXTURE OF SAID COMPOSITION.
 2. The composition of claim 1 wherein components (A) and (B) are present in quantities such that the NCO:OH ratio of the (A) and (B) components is from about 0.95:1 to about 1.1:1, component (C) is present in quantities of from about 30 to about 50 percent by weight of the sum of components (A), (B) and (C) and wherein component (D) is present in quantities of from about 0.5 to about 3 percent by weight of the sum of the weights of components (A), (B) and (C).
 2. placing the admixed composition into a suitable mold wherein said composition solidifies within less than about 5 minutes to a solid having the aforesaid density and elongation; and
 3. subsequently demolding the resultant article from the mold.
 3. The composition of claim 2 wherein component (D) is an organo-metal compound of a metal selected from tin, zinc, lead, mercury, cadmium, bismuth and antimony.
 4. The composition of claim 3 wherein component (C) is a cyclic carbonate or mixture thereof.
 5. The composition of claim 4 wherein component (C) is ethylene carbonate or propylene carbonate.
 6. The composition of claim 5 wherein component (D) is an organo-tin compound or an organo-lead compound.
 7. The composition of claim 3 wherein component (C) is an acyclic carbonate or mixture thereof.
 8. The composition of claim 7 wherein component (C) is bis(2-chloroethyl)carbonate.
 9. The composition of claim 8 wherein component (D) is an organo-tin compound or an organo-lead compound.
 10. The composition of claim 1 wherein component (D) is employed in quantities of from about 0.05 to about 2 percent.
 11. The composition of claim 1 wherein component (D) is employed in quantities of from about 0.1 to about 0.5 percent.
 12. The articles resulting from casting the compositiOns of claim
 1. 13. The articles of claim 12 wherein said articles are furniture components.
 14. The articles of claim 12 wherein said articles are decorative objects.
 15. The articles of claim 12 wherein said articles are machine components.
 16. A process for producing solid, rigid, polyurethane articles having a density of at least 1 g/cc, a percent elongation of less than 80, and which can be demolded within a period of about 5 minutes without the addition of an external source of heat which process comprises:
 17. The process of claim 16 wherein components (A) and (B) are present in quantities such that the NCO:OH ratio of the (A) and (B) components is from about 0.95:1 to about 1.1:1, component (C) is present in quantities of from about 30 to about 50 percent by weight of the sum of components (A), (B) and (C) and wherein component (D) is present in quantities of from about 0.5 to about 3 percent by weight of the sum of the weights of components (A), (B) and (C).
 18. The process of claim 17 wherein component (D) is an organo-metal compound of a metal selected from tin, zinc, lead, mercury, cadmium, bismuth and antimony.
 19. The process of claim 18 wherein component (C) is a cyclic carbonate or mixture thereof.
 20. The process of claim 19 wherein component (C) is ethylene carbonate or propylene carbonate.
 21. The process of claim 20 wherein component (D) is an organo-tin compound or an organo-lead compound.
 22. The process of claim 18 wherein component (C) is an acyclic carbonate or mixture thereof.
 23. The process of claim 22 wherein component (C) is bis(2-chloroethyl)carbonate.
 24. The process of claim 23 wherein component (D) is an organo-tin compound or an organo-lead compound.
 25. The process of claim 16 wherein component (D) is employed in quantities of from about 0.05 to about 2 percent.
 26. The process of claim 16 wherein component (D) is employed in quantities of from about 0.1 to about 0.5 percent.
 27. The process of claim 16 wherein said mold is that of a furniture component.
 28. The process of claim 16 wherein said mold is that of a decorative object.
 29. The process of claim 16 wherein said mold is that of a machine component. 